Sub-micron space liner and densification process

ABSTRACT

A method of depositing dielectric material into sub-micron spaces and resultant structures is provided. After a trench is etched in the surface of a wafer, an oxygen barrier is deposited into the trench. An expandable, oxidizable liner, preferably amorphous silicon, is then deposited. The trench is then filled with a spin-on dielectric (SOD) material. A densification process is then applied, whereby the SOD material contracts and the oxidizable liner expands. Preferably, the temperature is ramped up while oxidizing during at least part of the densification process. The resulting trench has a negligible vertical wet etch rate gradient and a negligible recess at the top of the trench.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to the field of integrated circuitfabrication, and more specifically to the deposition and processing ofspin-on dielectric materials.

2. Description of the Related Art

Integrated circuit manufacturers increasingly face difficulties withscaling. According to Moore's Law, the number of transistors per unit ofarea grows exponentially. For this to continue, several major changes insemiconductor manufacturing are expected. Transistors are not the onlydevices that must get smaller on an integrated circuit. Even thoughpacking transistors closer is important, they must still be electricallyseparated from each other. One method of keeping transistors separatefrom each other is known as trench isolation. Trench isolation is thepractice of creating trenches in the substrate in order to separateelectrical components on the chip. The trenches are filled with aninsulator that will prevent cross-talk between transistors.

Shallow Trench Isolation (STI) is becoming more prevalent in the designof integrated circuits. In STI, the trench width is becomingincreasingly smaller with successive generations. The size can vary, buta trench less than a micron wide has become quite common. STI shrinksthe area needed to isolate transistors from each other. STI also offerssmaller channel width encroachment and better planarity thantechnologies used for larger process nodes.

STI trenches are typically filled with oxide, but how that is donevaries. They can be filled by chemical vapor deposition (CVD), such ashigh-density plasma chemical vapor deposition (HDP CVD) using tetraethylorthosilicate (TEOS) as a precursor with or without ozone. However,filling these trenches with oxide gets more challenging as the width ofthe trenches gets smaller and aspect ratios thus increase. CVD depositsthe material from the outside of the trench inwards, leading to pinchingat the upper corners. This leads to problems such as the creation ofvoids, areas where the filler does not accumulate, or to seams where thegrowth from the sides of the edges meets. Such seams can createinconsistencies in subsequent processing, such as planarization or otheretch steps. HDP CVD methods can also result in undesired erosion ofunderlying features.

Another major method for filling isolation trenches is known as spin-ondeposition. Spin-on deposition entails dripping a liquid precursor ontothe wafer surface in a predetermined amount. The wafer is subjected torapid spinning (e.g., up to 6000 rpm). The spinning uniformlydistributes the liquid on the surface by centrifugal forces. The liquidfills low points and automatically planarizes the surface. Finally, thecoating is baked in order to solidify the material. While spin-on can bemore expensive and difficult to implement, it is seen as the long-rangesolution for the deposition of dielectric materials because of itsability to fill with no seam, void, or erosion problems.

However, there have been many problems with the implementation oftrench-fill systems. For the spin-on system, one of these problems hasbeen achieving acceptable bulk density in sub-micron STI trenches. Thereare some methods of achieving density in these sub-micron spaces,including the use of electron-beam and steam oxidation curing. However,available methods do not provide a full solution to the problems facedin this arena. For example, the inventors have found that known methodsof densification can lead to material that is too vulnerable to recessat the top of the trench during polishing and wet cleans. Thus, theavailable solutions do not fully address the problems related to thisarea.

SUMMARY OF THE INVENTION

In accordance with one aspect of the invention, a method is provided forcreating a shallow trench comprises etching a trench on a wafer. Themethod comprises depositing a liner on surfaces of the trench, fillingthe trench with a dielectric material, and densifying the dielectricmaterial with a process that will cause the liner to expand.

In another aspect of the invention, a method of densifying liquiddielectric material begins with curing a substrate in a curing chamberin a steam ambient environment. While the substrate is in the chamber,the temperature of the chamber is ramped up to a target temperature. Thesubstrate is then annealed at a temperature within a range of the targettemperature.

In another aspect of the invention, a amorphous silicon layer lines atrench. The trench is filled with a dielectric filler. The liner is thenexpanded while the filler is contracted.

In another aspect of the invention, an amorphous silicon layer lines atrench. The trench is filled with a dielectric filler. The liner is thenexpanded while the filler is contracted.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other aspects of the invention will be better understood fromthe Detailed Description of the Preferred Embodiments and from theappended drawings, which are meant to illustrate and not to limit theinvention, and wherein:

FIG. 1 is a schematic, cross-sectional side view of the substrate with athin “pad oxide” grown over the surface of the substrate, a thickerlayer of silicon nitride (Si₃N₄), and a photoresist mask in accordancewith a starting point for preferred embodiments of the presentinvention.

FIG. 2 is a schematic, cross-sectional side view of the substrate ofFIG. 1 after a trench has been formed with a reactive ion etch (RIE).

FIG. 3 is a schematic, cross-sectional side view of the substrate ofFIG. 2 with thin oxide, nitride, and amorphous silicon layers lining thetrench.

FIG. 4 is a schematic, cross-sectional side view of the substrate ofFIG. 3 with a layer of spin-on dielectric material filling the trench.

FIG. 5 is a schematic, cross-sectional side view of the substrate ofFIG. 4 after a curing and densification process.

FIG. 6 is a schematic, cross-sectional side view of the substrate ofFIG. 5 after chemical mechanical polishing (CMP) the oxide down to thetop nitride surface.

FIG. 7 is a flow chart of a process for shallow trench isolation inaccordance with the preferred embodiment.

FIG. 8 is a flow chart of a process for densification of spin-ondielectric in accordance with the preferred embodiment of the presentinvention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Bulk density of spin-on dielectric (SOD) materials can be achieved insub-micron spaces, such as isolation trenches, through the use of aliner material that expands irreversibly when oxidized. In theillustrated embodiments described below, after a trench is formed, thesidewalls of the trench are oxidized, and a nitride layer is depositedto protect the active area of the trench. An expandable liner isdeposited over the nitride liner before the trench is filled with adielectric material. When the dielectric material is densified, theliner expands. The dielectric material reduces in size significantly asthe material is densified. The expanding liner serves to evenly compressthe dielectric material. In this manner, the combination of the linerand the densification process yields excellent bulk density insub-micron spaces.

The liner material is preferably easily deposited in small spaces andirreversibly expanded when oxidized. In a preferred embodiment, theliner is amorphous silicon. As amorphous silicon oxidizes into siliconoxide, it expands. Other materials that expand upon oxidation, such aspolysilicon, could also be used.

The densification of the materials within sub-micron spaces is alsohelpful to the proper filling of the space. In a preferred embodiment,the wafer is cured in a steam chamber. While the wafer is in thechamber, the temperature is increased. After the temperature reaches thetarget, the wafer anneal continues at a temperature plateau. Thedensification process has the benefit of densifying the spin-on materialsufficiently without damaging any of the surrounding materials. Abeneficial result of this densification process is the matching of wetetch resistance in small and large features.

In order to attain better bulk density in small spaces, such as spacessmaller than a micron in width, improvements are made to the process ofdepositing these materials. Spin-on deposition is preferably used inorder to avoid creating a seam in the deposited material. The skilledartisan, however, will readily find application for the principles andadvantages taught herein to the use of other filler materials withintrenches in a variety of fabrication contexts.

Creating the Sub-Micron Space

An introductory step is the creation of a sub-micron space, such as atrench for shallow trench isolation (STI). As shown in FIG. 1, asemiconductor substrate 10, e.g., a silicon wafer, is provided and athin “pad” oxide 12 is thermally grown on the substrate. Afterward athick layer of a silicon nitride 14, preferably Si₃N₄, is formed. Thenitride 14 is preferably formed by chemical vapor deposition (CVD). Thisnitride layer 14 acts as a stop for the chemical mechanical polishing(CMP) process. Exemplary thickness ranges are between about 30 Å and 100Å for the pad oxide 12 and between about 200 Å and 1500 Å for thenitride layer 14.

As shown in FIG. 1, a photoresist mask 16 is applied to the substrate 10in order to etch the trench. Photoresist is applied on the surface ofthe wafer. A reticle that blocks ultraviolet (UV) radiation is thenplaced over the wafer. The photoresist is then selectively exposed to UVradiation. Depending upon whether positive or negative resist isemployed, the developing solution washes away either exposed orunexposed regions. After the trench is etched, the photoresist mask 16of FIG. 2 is removed by conventional resist strip process.

A trench can be etched in two primary ways, isotropically oranisotropically. The anisotropic method is directional and producesrelatively straight, vertical sidewalls. One type of anisotropic etch isknown as reactive ion etch (RIE). As shown in FIG. 2, this method isquite accurate and straight; however, it damages sidewalls 18 of thetrench, which define edges of transistor active areas. As shown in FIG.3, the sidewalls 18 are preferably oxidized, forming a thin oxide layer24, in order to repair the damage from the prior RIE.

Filling the Trench

In order to protect the active areas adjacent to the trench fromsubsequent processing, an insulating oxygen barrier, in the illustratedembodiment comprising another nitride layer 20, is deposited in thetrench, preferably by CVD. This layer can range in thickness ofpreferably between about 10 angstroms (Å) and 300 Å, more preferablybetween about 20 Å and 200 Å, and most preferably between about 30 Å and150 Å. The nitride layer 20 both protects the active area and acts as anoxygen barrier between the semiconductor layer and the filler materials.

As shown in FIG. 3, a thin expandable liner layer 22 is formed in thetrench. This liner layer 22 can be formed in several ways, but the layeris preferably deposited using CVD. The liner material preferably expandsduring a densification process described below. In a preferredembodiment, the liner preferably comprises amorphous silicon with athickness of between about 20 Å and 200 Å, more preferably between 25 Åand 150 Å, most preferably between 50 Å and 100 Å. Preferably, the lineris completely oxidized during the densification process described below.Because amorphous silicon is easy to apply using CVD and expandsrelatively uniformly upon oxidation, it makes an excellent liner layer22. Additionally, amorphous silicon makes a high quality oxide whenoxidized.

A spin-on deposition process is preferably used to deposit a dielectricmaterial 26 into the remaining space in the trench, as shown in FIG. 4.The thickness of this layer 26 will vary based upon the size of thetrench, but in the illustrated embodiment the thickness of the materialis preferably between 2500 Å and 5500 Å, more preferably between 3000 Åand 4500 Å. Spin-on deposition uses liquid materials placed on a wafer.The wafer is then rapidly spun, which spreads the liquid uniformly overthe surface of the wafer after filling the low points on the wafer. Anexample of a spin-on material is Spinfil™ made by Clariant (Japan)K.K.—Life Science & Electronic Chemicals of Tokyo, Japan. However, theskilled practitioner will appreciate that many dielectric materials canbe used for these purposes.

Other processes, such as TEOS CVD, can also be used to fill the trench.While filling by CVD would not yield the best possible results, theamorphous silicon liner could also be beneficial for this process. Theamorphous silicon liner would expand upon oxidation, compressing theTEOS filler. Skilled practitioners will appreciate that severaldeposition processes could be used to fill the trench.

Densification Process

The densification process recommended by Clariant, the manufacturer ofthe spin-on dielectric (SOD) material, was found unsatisfactory for thepurposes of such small spaces. Clariant's Spinfil™ SOD material, basedupon perhydrosilazane (SiH₂NH), has a recommended baking recipe asfollows:

1) 3 min of hot plate baking at 150° C.,

2) 30 min at 700–800° C. in steam ambient

3) Annealing for STI at 800–1000° C. in dry oxygen.

However, this process was found problematic for trenches that are verysmall, particularly where trenches of a variety of widths across thesubstrate are to be filled. With this process, during the subsequentetchings, CMP, and wet cleans, the trench-fill material has been foundto recess too much. Also, the wet etch rates and density of the materialwithin the trench after the densification was not consistent from thetop to the bottom as in larger features. A new process was needed inorder to correct the problems. The process preferably densifies thematerial enough so that it does not recess excessively when beingplanarized, etched, or wet cleaned. This preference must also bebalanced by the need for the densification process to be mild enough toavoid oxidizing the nitride layer in addition to the SOD material andthe amorphous silicon layer. If the nitride layer is oxidized, thesemiconductor sidewalls that define the edges of transistor active areascould also be subsequently oxidized, thereby consuming criticaltransistor real estate. Also, preferably, the materials within thetrench should not significantly shrink away from the walls much.

A preferred embodiment of a densification process is shown in flow chartform in FIG. 8. Preferably, 200 a prepared wafer is placed in a chamber.The wafer is preferably heated 210 to an initial temperature of betweenabout 200° C. and 600° C., more preferably between 300° C. and 500° C.,most preferably between 350° C. and 450° C. in the chamber. Preferably,steam is then turned on 220 in the chamber. From the initialtemperature, the heat ramps 230 up to a target temperature betweenapproximately 800° C. and 1200° C., more preferably between 900° C. and1100° C., and most preferably between 950° C. and 1050° C. The increaseof the temperature in the chamber is stopped 240 when it gets to thistarget temperature. The temperature can increase approximately betweenabout 3° C. per minute to 25° C. per minute, more preferably betweenabout 8° C. and 20° C. During the escalation of the temperature, thewafer is in an oxidizing environment, preferably an ambient steamenvironment. After the temperature is ramped up, the wafer is annealed250 for approximately 10 to 40 minutes, more preferably between 15 minand 35 min, at the temperature plateau on steady state. In the preferredembodiment, the wafer is annealed in a second oxidizing environment,preferably in a dry oxygen (O₂) environment. Finally, after the processis done, the wafer is removed 260 from the chamber.

In this process the steam reacts with the polysilizane on the heatedsubstrate. As the temperature rises, the reaction begins to increase therate of oxidation. The chemical reaction associated with the densifyingprocess of the preferred spin-on dielectric, polysilizane, is shownbelow:Si_(x)N_(y)H_(z)+H₂O→SiO₂+H₂+NH₃

FIG. 5 shows the trench and surrounding area after the densificationprocess. During the densification process, a linear volume decrease ofpreferably about 7% to 25%, or more preferably between about 12% and18%, takes place. In other words, the volume of the spin-on dielectricmaterial will shrink linearly by approximately 15% as it turns into alayer of silicon oxide 32. In the preferred embodiment, the process willoxidize both the SOD material and the amorphous silicon liner. As theSOD material oxidizes and shrinks, the preferred amorphous silicon layerwill expand as it turns into a layer of liner silicon oxide 30. If thethickness of the amorphous silicon layer is selected properly, theentirety of the layer will be consumed during the oxidation. The nitrideliner 20 below the liner will not be oxidized because the oxidationprocess is not that aggressive, and furthermore the liner 20 preferablygetters excess oxidant. Both the SOD material and the liner will becomeforms of silicon oxide in the densification process. However, the fillersilicon oxide 32 that was the SOD material may etch faster than theliner silicon oxide 30 that was the amorphous silicon liner.

The expandable liner 22 of FIG. 4 serves to compress the dielectricmaterial evenly. The liner's functions include compressing thedielectric materials evenly and acting as a getter of oxygen for thedielectric material during the densification process. As the preferredamorphous silicon layer 22 is oxidized, it expands uniformly from itsposition along the sidewalls of the trench, evenly compressing thedielectric material. This reinforces the constant wet etch rate in eachof the sections of silicon oxide from the top of the trench to thebottom of the trench.

Structure

As shown in FIG. 6, a CMP or other etchback process can be used toremove undesired materials on top of the wafer. The consistent and slowetch rates in the layers of silicon oxide 30, 32 substantially reducesany recess formed at the top of the trench. The nitride layer 20 in thetrench remains in the trench after the densification process to protectthe active areas adjacent to the trench.

When used in combination, the liner and the densification process yieldtwo silicon oxide layers that have a neglible vertical wet etch rategradient. In other words, the wet etch rate is substantially consistentfrom the top to the bottom of the trench in each of the layer.Typically, a narrower trench will have a bigger gradient. However, thiswas not the case for the preferred process described above when both theamorphous silicon liner and the densification process were used. Theeven compression by the liner creates substantial uniformity of wet etchrate gradients in the densified dielectric material from trench totrench, even when one trench is significantly narrower. For example, atrench with a width of w will have a substantially similar wet etch rategradient in the filler silicon oxide 32 as a trench with a width of 3 w,5 w, or even 10 w. In a preferred embodiment, the vertical etch rategradient of two trenches of widths varying by an order of magnitude iswithin 5%, more preferably within 2%. This consistency is helpful whenperforming etches, CMPs, and wet cleans across an entire wafer.

Additionally, because the SOD system is used, the filler material doesnot have a seam as would result if the trench were filled using CVDprocess such as ozone TEOS. This avoids problems with subsequentprocessing, including planarizations and etches.

FIG. 6 shows the structure after the process is completed and the waferhas been through etching and a wet clean. It can be seen that there asubstantially reduced recess on the top of the shallow trench. Thenitride liner 20 is not oxidized beneath the silicon oxide. There aretwo identifiable layers of silicon oxide in the trench. The first,thinner liner oxide layer 30 is a thermal oxide formed from theamorphous silicon liner. The second filler oxide layer 32 is the thickerlayer of silicon oxide, which is a spin-on dielectric. It typically hasa higher wet etch rate than that of the thermal oxide in small features.

If the liner 22 is used without the improved densification process orthe densification process is used without the liner 22, benefits arestill obtained. The problems of wet etch rate gradient and recessing atthe top of the trench will still be less than that if neitherimprovement were used. In a preferred embodiment shown in FIG. 7, bothof these improvements are used in order to maximize the benefit gainedfrom the improvements.

It will be appreciated by those skilled in the art that variousomissions, additions and modifications may be made to the methods andstructures described above without departing from the scope of theinvention. All such modifications and changes are intended to fallwithin the scope of the invention, as defined by the appended claims.

1. A method of creating a trench isolation structure, the methodcomprising etching a trench in a substrate, wherein the trench has abase and walls; depositing a liner on surfaces of the trench; fillingthe trench with a dielectric material; and densifying the dielectricmaterial with a process that will cause the liner to expand, whereindensifying comprises ramping the substrate temperature from an initialtemperature to a target temperature in an oxidizing environment.
 2. Themethod of claim 1, further comprising growing a layer of thermal oxideon the surface of the wafer before etching the trench.
 3. The method ofclaim 2, further comprising depositing a layer of silicon nitride overthe thermal oxide before etching the trench.
 4. The method of claim 1,wherein etching comprises reactive ion etching (RIE).
 5. The method ofclaim 4, further comprising oxidizing the walls of the trench after RIE.6. The method of claim 1, further comprising depositing a nitride layeron the substrate before depositing the liner and after etching thetrench.
 7. The method of claim 6, wherein the nitride layer is betweenabout 10 Å and 300 Å thick.
 8. The method of claim 1, further comprisingdepositing an insulating oxygen barrier layer before depositing theliner after etching the trench.
 9. The method of claim 1, wherein theliner expands upon oxidation.
 10. The method of claim 1, wherein theliner comprises amorphous silicon.
 11. The method of claim 10, whereinthe amorphous silicon liner is between 2 Å and 200 Å thick.
 12. Themethod of claim 10, wherein the amorphous silicon liner is between 50 Åand 100 Å thick.
 13. The method of claim 1, wherein filling comprisesapplying a liquid to the substrate.
 14. The method of claim 1, whereinfilling comprises using a spin-on deposition process.
 15. The method ofclaim 1, wherein filling comprises using a chemical vapor depositionprocess.
 16. The method of claim 1, wherein densifying the dielectricmaterial causes a linear volume decrease of the dielectric material ofbetween about 7% and 25%.
 17. The method of claim 16, wherein densifyingthe dielectric material causes a linear volume decrease of thedielectric material of between about 12% and 18%.
 18. The method ofclaim 1, wherein densifying the dielectric material comprises oxidizingthe dielectric material.
 19. The method of claim 1, wherein expandingthe liner is performed by oxidizing the liner.
 20. The method of claim19, wherein oxidizing comprises curing in a steam ambient environment ina curing chamber.
 21. The method of claim 1, wherein the initialtemperature is between about 200° C. and 600° C.
 22. The method of claim21, wherein the target temperature is between about 800° C. and 1200° C.23. The method of claim 1, wherein ramping comprises increasing thesubstrate temperature at a rate of between about 3° C. and 25° C. perminute.
 24. The method of claim 20, wherein ramping comprises increasingthe substrate temperature at a rate of between about 8° C. and 20° C.per minute.
 25. The method of claim 20, wherein densifying furthercomprises annealing the substrate for between about 10 and 40 minutes ata temperature between about 800° C. and 1200° C. after ramping.
 26. Themethod of claim 25, wherein annealing is done in an oxygen environment.27. The method of claim 1, wherein the oxidizing environment comprises asteam ambient environment.
 28. A method of densifying liquid dielectricmaterial, the method comprising: curing a dielectric material on asubstrate in a curing chamber in a steam ambient environment, whereinthe temperature in the curing chamber ramps from an initial temperatureof between about 200° C. and 600° C. to a target temperature of betweenabout 800° C. and 1200° C. at a rate of between about 3° C. and 25° C.per minute while the substrate is in the curing chamber; and annealingthe substrate at a temperature of between about 800° C. to 1200° C. forbetween 10 and 40 minutes after the substrate has been cured.
 29. Themethod of claim 28, further comprising filling a trench with adielectric material before curing the dielectric material.
 30. Themethod of claim 29, wherein filling comprises spin-on deposition. 31.The method of claim 28, wherein densifying the dielectric materialcauses a linear decrease of the dielectric material between about 7% and25%.
 32. The method of claim 31, wherein densifying the dielectricmaterial causes a linear decrease of the dielectric material betweenabout 12% and 18%.
 33. The method of claim 29, further comprisingexpanding a amorphous silicon liner between trench walls and thedielectric material while densifying the dielectric material.
 34. Themethod of claim 28, wherein annealing is performed in an oxidizingenvironment.
 35. The method of claim 28, wherein annealing is performedin a dry oxygen environment.
 36. A method of isolating electricalcomponents on an integrated circuit, comprising: lining a trench on asubstrate with an expandable liner; filling the trench with a dielectricfiller; and expanding the liner while contracting the dielectric fillerusing a process comprising curing the substrate in a steam ambientenvironment at a temperature between about 200° C. and 600° C. andramping up to a temperature between about 800° C. and 1200° C.
 37. Themethod of claim 36, further comprising lining the trench with an oxygenbarrier before lining the trench with the expandable liner.
 38. Themethod of claim 36, wherein the oxygen barrier comprises siliconnitride.
 39. The method of claim 36, wherein the expandable liner isamorphous silicon.
 40. The method of claim 36, wherein the dielectricfiller is applied as a liquid.
 41. The method of claim 40, whereinfilling comprises spin-on deposition.
 42. The method of claim 36,wherein expanding the liner while contracting the dielectric fillercomprises oxidizing the liner.
 43. The method of claim 42, whereinexpanding the liner while contracting the dielectric filler furthercomprises oxidizing the dielectric filler.
 44. The method of claim 36,wherein ramping comprises increasing the substrate temperature at a rateof between about 3° C. and 25° C. per minute.
 45. The method of claim36, wherein the process further comprises annealing at a temperature ofbetween about 800° C. and 1200° C. for approximately 10 to 40 minutesafter ramping up.
 46. The method of claim 45, wherein annealing isperformed in an oxidizing environment.
 47. The method of claim 45,wherein annealing is performed in a dry oxygen environment.
 48. Themethod of claim 36, wherein contracting the dielectric filler comprisesa linear volume decrease of the dielectric filler between about 7% and25%.
 49. The method of claim 48, wherein contracting the dielectricfiller comprises a linear volume decrease of the dielectric fillerbetween about 12% and 18%.